CN106413920B

CN106413920B - Method for coating a metal surface of a substrate and article coated according to the method

Info

Publication number: CN106413920B
Application number: CN201580020675.5A
Authority: CN
Inventors: W.布雷姆泽; M.德罗尔; O.泽瓦尔德; E.尼森-瓦尔肯廷; L.沙赫特西克; M.特劳特; M.施万布; D.瓦泽法伦; V.佐特克; A.弗伦克尔; R.艾林霍夫; S.格罗尔德; N.克尔法拉
Original assignee: Chemetall GmbH
Current assignee: Chemetall GmbH
Priority date: 2014-02-27
Filing date: 2015-02-27
Publication date: 2020-03-27
Anticipated expiration: 2035-02-27
Also published as: RU2701019C2; RU2016138171A; AU2015222090A1; JP2017514011A; KR102399225B1; RU2016138171A3; KR20160127091A; BR112016019705A2; US11389823B2; JP6645976B2; ZA201606675B; DE102015203507A1; BR112016019705B1; MX2016011120A; US20170066009A1; SG11201607140XA; WO2015128449A1; EP3110566A1; AU2015222090B2; EP3110566B1

Abstract

The invention relates to a method for coating a metal surface of a substrate with an aqueous composition, hereinafter also referred to as coating composition, in the form of a dispersion and/or suspension, which contains at least one stabilized binder and gelling agent and forms an ionic gel-based coating with cations that dissolve out of the metal surface in a pretreatment step and/or during contact, in which method the coating is carried out by: I. providing a substrate having a cleaned metal surface, ii. contacting and coating the metal surface with a first aqueous composition in the form of a dispersion and/or suspension, iii. optionally rinsing the organic coating, iv. optionally drying the organic coating, and v. coating with at least one further coating composition before drying and crosslinking all applied coatings, wherein the stabilized binder must satisfy the condition that a) the aqueous mixture consists of deionized water, 0.2 to 2 wt.% of a gelling agent and 5 to 20 wt.% of the stabilized binder; b) adjusting to a pH value of 1 to 7; c) immersing the cleaned substrate in the mixture according to b) at room temperature for at least 1 minute, and d) testing whether deposition of an organic coating of at least 1 μm has occurred, wherein e) an additional test is carried out in the absence of a gelling agent, wherein a mixture consisting of deionized water and 5 to 20% by weight of the dispersion to be tested is prepared; f) the mixture prepared in e) is likewise adjusted to a pH value of 1 to 7, and g) the tests described in c) and d) are repeated.

Description

Method for coating a metal surface of a substrate and article coated according to the method

Technical Field

The invention relates to a method for coating a surface, to a corresponding coating and to the use of an object coated according to the method. There are numerous methods for producing uniform coatings on surfaces, in particular of metals, by means of dipping methods. The following techniques are preferably used here for producing, in particular, corrosion protection coatings which consist essentially of an organic matrix and organic and/or inorganic additional components.

Background

The traditional approach is based on the application of rheological properties to the formulations used to achieve a complete coating of the joined workpieces. Although the accumulation of coating material at critical points can be reduced by continuing to rotate the relevant workpiece after the dipping process, it is not possible to achieve a completely uniform coating by this method. Additionally, defects such as blisters and craters (Kocher) can occur at locations with higher coating content during drying and/or crosslinking, which impair the quality of the overall coating.

The electrophoretic method avoids these problems by using an electric current, so that a uniform coating is deposited upon dipping.A largely uniform coating is successfully produced on the metal workpiece using this method.A deposited coating exhibits particularly good adhesion to the metal substrate in the wet state, whereby the workpiece can be treated in a subsequent rinsing step without peeling off the coating.A disadvantage is that the above-mentioned inaccessible locations on the workpiece are freed from excess lacquer solution and therefore no defects occur during the drying process.A disadvantage is that, in addition to the required amount of electrical energy and the appropriate dipping bath, which lead to an increase in costs, so-called edge bleeding (Kantenfluence) occurs, since electrostatic fields are not formed uniformly at the macroscopic edges and the edges are coated uniformly and possibly even incompletely.

The known autophoresis is based on the currentless concept consisting of an acid-wash attack on the surface of the substrate used, in which metal ions dissolve out of the surface and the emulsion coagulates due to the concentration of metal ions at the resulting interface. Although this method does not have the above-mentioned limitations of the electrolytic method with regard to the faraday cage effect, the coating produced in the process has to be fixed in a complicated multi-step dipping process after the first activation step. Furthermore, the pickling attack leads to an unavoidable contamination of the active zone with metal ions, which must be removed from the zone. Furthermore, the method is based on a chemical deposition process, which cannot be self-regulated and, if necessary, cannot be interrupted by switching off the current, as in the case of the electrolytic method. Thus, in the case where the metal base material stays in the active region for a long time, it is inevitable to form an excessively high thickness of the clad layer.

The efficient and economical formation of a uniform coating during impregnation has long been a desire to produce coatings of as large a thickness as possible which are as closed and substantially flat as possible.

DE 102014213873 a1 discloses a method for coating a substrate and an article coated according to the method, in which a cleaned surface of the substrate is contacted and coated with an aqueous composition in the form of a dispersion or/and suspension, and after drying the organic coating, the coating with a coating composition of the same type or another can be carried out before drying or/and baking. An important feature of the process is that the substrate is covered with a sol or silane-or silicate-modified polymer of a colloidal silicate in which polyvalent metal cations are embedded prior to coating with the aqueous composition in the form of a dispersion or/and suspension.

Disclosure of Invention

The invention relates to a method for coating a metal surface of a substrate with an aqueous composition, hereinafter also referred to as coating composition, in the form of a dispersion and/or suspension, which contains at least one stabilized binder and gelling agent (gellbildner) and forms an ionic gel-based coating with cations that dissolve out of the metal surface in a pretreatment step and/or during contact, in which method the coating is carried out by:

I. providing a substrate having a cleaned metal surface,

contacting and coating the metal surface with a first aqueous composition in the form of a dispersion and/or suspension,

optionally rinsing the organic coating layer,

optionally drying the organic coating, and

v. coating with at least one further coating composition before drying and crosslinking all applied coatings, wherein the stabilized binder must satisfy the following conditions,

a) the aqueous mixture consists of deionized water, 0.2 to 2 weight percent gelling agent, and 5 to 20 weight percent stabilized binder;

b) adjusting to a pH value of 1 to 7;

c) immersing the cleaned substrate in the mixture according to b) at room temperature for at least 1 minute, and

d) it was tested whether a deposition of an organic coating of at least 1 μm occurred, wherein,

e) an additional test was carried out in the absence of gelling agent, in which a mixture consisting of deionized water and 5 to 20% by weight of the dispersion to be tested was prepared;

f) the mixture prepared in e) is likewise adjusted to a pH value of from 1 to 7, and

g) the tests described under c) and d) were repeated.

It has surprisingly been found that a substrate having a metal surface forms an ionic gel-based coating with cations that dissolve out of the metal surface during contact when treated with an aqueous composition of a stabilized binder and a gelling agent selected according to the invention and that the ionic gel coating deposited on the substrate allows diffusion through of further cations that dissolve out of the metal surface, so that coating with further coating compositions according to the invention can be carried out in further coating baths/steps.

Preferably, a stabilized binder is selected which satisfies the condition,

a) the aqueous mixture consists of deionized water, 0.3 to 1 weight percent gelling agent, and 7 to 15 weight percent stabilized binder;

b) adjusting the pH value to a value of 1.5 to 5 with the aid of a mineral acid;

c) immersing the cleaned substrate in the mixture according to b) at room temperature for 2 to 15 minutes, and

d) it was tested whether a deposition of an organic coating of at least 2 μm occurred, wherein,

e) an additional test was carried out in the absence of gelling agent, in which a mixture consisting of deionized water and 7 to 15% by weight of the dispersion to be detected was prepared;

f) the mixture prepared in e) is likewise adjusted to a pH value of 1.5 to 5 with the aid of mineral acids, and

g) the tests described under c) and d) were repeated.

The stabilized binder is particularly preferably selected from: non-ionically stabilized polyepoxy dispersions, non-ionically stabilized polyurethane dispersions and ionically stabilized polyacrylate dispersions.

Preferably, the aqueous composition contains 0.01 to 80.0 wt.%, based on the total mass of the resulting mixture, of a stabilized dispersion and 0.001 to 20.0 wt.%, based on the total mass of the resulting mixture, of at least one gelling agent, wherein the stabilized dispersion has a solids content of 20 to 90 wt.%, a viscosity of 100 to 5000mPas, and a density of 1.0 to 1.2g/cm³And a pH-value in the range of 0.5 to 10.

Particularly preferably, the aqueous composition further contains one or more representatives from the group:

a) a crosslinking agent selected from silanes, siloxanes, phenolic resins or amines in an amount of 0.01 to 50g/L,

b) complexed titanium fluoride and/or zirconium fluoride in an amount of 0.01 to 50g/L,

c) a content of at least one defoamer, and

d) at least one additive selected from the group consisting of: pigments, biocides, dispersion auxiliaries, film-forming auxiliaries, auxiliaries for adjusting the pH value, thickeners and levelling agents.

Preferably, the gelling agent contains or consists of a component selected from the group consisting of: a) at least one polysaccharide based on glycogen, amylose, amylopectin, guaiacol, agar, algin, alginate, pectin, carrageenan, cellulose, chitin, chitosan, curdlan, dextran, levan, collagen, gellan gum, gum arabic, starch, xanthan gum, tragacanth gum, karaya gum (Karayanen), Tarakernmehlen and glucomannan; b) at least one anionic polyelectrolyte of natural origin, based on polyamino acids, collagen, polypeptides, lignin, or c) at least one synthetic anionic polyelectrolyte, based on polyamino acids, polyacrylic acid-copolymers, acrylamide-copolymers, lignin, polyvinylsulfonic acids, polycarboxylic acids, polyphosphoric acids or polystyrene.

It is particularly preferred that the aqueous composition and the organic coating prepared therefrom contain at least one anionic polysaccharide selected from the group of carboxyl functions having a degree of esterification in the range of from 5 to 75%, based on the total number of alcohol-and carboxyl groups.

Quite particularly preferably, the aqueous composition and the organic coating prepared therefrom contain at least one anionic polysaccharide or at least one anionic polyelectrolyte selected from those having a molecular weight of from 500 to 1000000g/mol^-1Within the range of (a).

The aqueous composition and the organic coating prepared therefrom contain at least one anionic polysaccharide or at least one anionic polyelectrolyte selected from the group consisting of those having a degree of amidation of the carboxyl functions in the range of from 1 to 50% or a degree of epoxidation of the carboxyl functions of up to 80%.

Preferably, the anionic polyelectrolyte is modified with an adhesion group selected from the group consisting of multifunctional epoxides, isocyanates, primary amines, secondary amines, tertiary amines, quaternary amines, amides, imides, imidazoles, formamides, Michael reaction products, carbodiimides, carbenes, cyclic carbonates, multifunctional carboxylic acids, amino acids, nucleic acids, methacrylamides, polyacrylic acids, polyacrylic acid derivatives, polyvinyl alcohols, polyphenols, polyols bearing at least one alkyl and/or aryl group, caprolactams, phosphoric acids, epoxy esters (Epoxidern), sulfonic acids, sulfonic esters, vinylsulfonic acids, vinylphosphonic acids, catechols, silanes, and silanols and/or siloxanes formed therefrom, triazines, thiazoles, thiazines, dithiazines, acetals, hemiacetals, quinones, saturated fatty acids, unsaturated fatty acids, alkyds, esters, polyesters, ethers, diols, cyclic ethers, crown ethers, anhydrides, and acetylacetone and β -diketones, carbonyls and hydroxyls.

It is particularly preferred that the aqueous composition and the organic coating prepared therefrom have a content of at least one complexing agent for metal cations or a polymer modified to complex metal cations.

Quite particularly preferably, the aqueous composition and the organic coating prepared therefrom have a content of at least one complexing agent selected from the group of maleic, alendronic, itaconic, citraconic or mesaconic acid or anhydrides or half-esters of these carboxylic acids.

The aqueous composition and the organic coating produced therefrom contain at least one type of cation selected from the group of salts based on cations, selected from melamine salts, nitroso salts, oxonium salts, ammonium salts, salts with quaternary nitrogen cations, salts of ammonium derivatives and metal salts of Ag, Al, Ba, Ca, Co, Cu, Fe, In, Mg, Mn, Mo, Ni, Pb, Sn, Ta, Ti, V, W, Zn or/and Zr.

Preferably, the aqueous composition contains a crosslinking agent selected from silanes, siloxanes, phenolics or amines in an amount of 0.01 to 50 g/L.

Particularly preferably, the aqueous composition contains complexed titanium fluoride and/or zirconium fluoride in an amount of from 0.01g/L to 50 g/L.

Particularly preferably, the aqueous composition contains complexed titanium fluoride and/or zirconium fluoride in an amount of from 0.1g/L to 30 g/L.

The aqueous composition has an amount of at least one defoamer.

The aqueous composition may furthermore contain at least one additive selected from: pigments, biocides, dispersion auxiliaries, film-forming auxiliaries, auxiliaries for adjusting the pH value, thickeners and levelling agents.

Preferably, the metal surface is cleaned, pickled or pretreated before contacting and coating it with the aqueous composition in process step II.

Preferably, in the method according to the invention, each of the aqueous compositions forms an ionic gel-based coating, wherein the coating thickness of all deposited coatings is in the range of 3 to 500 μm, preferably 5 to 300 μm and particularly preferably 8 to 100 μm after drying and crosslinking all applied coatings and 2 to 10, preferably 3 to 5 coatings are deposited.

Each organic coating is formed in the immersion bath within 0.05 to 20 minutes and, after drying, has a dry film thickness in the range from 1 to 100 μm, preferably from 3 to 60 μm and particularly preferably from 5 to 30 μm.

The invention also relates to an aqueous composition for use in the method according to the invention, each consisting of a mixture of at least one stabilized dispersion and a gelling agent, the dispersion having a solids content of from 30 to 90% by weight, a viscosity of from 100 to 5000mPas and a viscosity of from 1.0 to 1.2g/cm³In an amount of 0.01 to 80.0 wt. -%, based on the total mass of the obtained mixture, and in an amount of 0.001 to 20.0 wt. -%, based on the total mass of the obtained mixture, of the gelling agent, wherein the aqueous composition has a pH-value in the range of 1 to 7.

Preferably, the aqueous composition further contains one or more representatives selected from the group consisting of:

c) a content of at least one defoamer, and

The coating according to the invention can preferably be used for coated substrates as wire, wire gauze, strip, plate, profile, lining, parts of motor vehicles or aircraft, household appliance elements, elements in the building industry, frames, guard rail elements, heater elements or fence elements, mouldings of complex geometry or small parts such as, for example, screws, nuts, flanges or springs. The coatings are particularly preferably used in automotive engineering, in the construction industry, in the manufacture of devices, in household appliances or in the manufacture of heating devices. The use of the method according to the invention is particularly preferred for coating substrates which are problematic when coating with electrophoretic dip coatings.

Detailed Description

The invention is described in more detail below with the aid of examples, without thereby limiting the general teaching of claim 1 according to the invention.

Examples

The materials used and the implementation of the methods are first described generally.

A. Base material:

1: an electrolytically galvanized steel sheet having a zinc coating covering of 5 μm, a sheet thickness of 0.81 mm,

2: cold rolled steel, the thickness of the plate is about 0.8 mm,

3: quality grade AC 170 aluminum alloy, plate thickness about 1.0 mm.

B. Alkali washing:

1: 30g/L Gardocleen S5176 and 4 g/LGardobond Additiv H7406 of Chemetall GmbH are prepared in urban water. The plate was purged 180s at 60 ℃ in a spray bath and subsequently rinsed 120s in an immersion bath with city water and 120s in an immersion bath with deionized water.

C. Pretreatment:

1: pretreatment based on zinc phosphate (Gardobond 26S from Chemetall GmbH)

2: silane-based pretreatment (Oxsilan 9810/2 from Chemetall GmbH)

Coating a surface with a formulation according to the invention for forming an organic coating:

all mixtures were applied to the respective substrates at room temperature within 5 minutes by means of an immersion bath.

D. Ingredients of formulations

All data in the following table represent the weight fractions in percent in the form of the supply of the components. The percentage of deionized water contained corresponds to the difference between the sum of the contents given in the table and 100% by weight.

a) Binder used (Polymer-Dispersion/suspension)

1: dispersion A

Non-ionically stabilized polyepoxy dispersions having a solids content of from 45 to 49%, a pH value of from 5.0 to 6.0, a viscosity of from 1000-³The density of (c).

2: dispersion B

Non-ionically stabilized polyurethane dispersions having a solids content of 30%, a pH value of 3.0 to 6.0, a viscosity of 300-2000 mPas and 1.1 g/cm³The density of (c).

3: dispersion C

Ionically stabilized polyacrylate dispersion having a solids content of 50%, a pH value of 7.5 to 8.5, a viscosity of 200mPas, 1.05 g/cm³The density of (c).

b) Gelling agents used

1: gelling agent A

A 1:1 mixture of a polysaccharide having a molecular weight of about 70000 g/mol, a degree of amidation of 11%, a degree of esterification of 10%, a degree of epoxidation of 0%, a galacturonic acid content of 88% and a polysaccharide having a molecular weight of about 70000 g/mol, a degree of amidation of 0%, a degree of esterification of 38%, a degree of epoxidation of 0%, a galacturonic acid content of 85% was used as gelling agent. To prepare the formulation, a 2% aqueous solution of the polysaccharide was used.

2: gelling agent B

Polysaccharides having a molecular weight of about 70000 g/mol, a degree of amidation of 0%, a degree of esterification of 15%, a degree of epoxidation of 0%, a galacturonic acid content of 85% were used as gelling agents. To prepare the formulation, a 2% aqueous solution of the polysaccharide was used.

c) Pigment (I)

1: gas black-RCC pigment paste based on dispersion resins for aqueous coating systems, having a pH in the acidic range, a pigment content of 4%, a filler content of 50%, and a dispersion additive content of 10%, wherein the solids content obtained is about 60%

2: micronized white pigments based on titanium dioxide-rutile, their inorganic and organic coating

3: iron oxide red, hiding, as an aqueous dispersion, color index pigment Red 101/77491, pH-7-10 and density 1.7 to 1.9 g/cm³

Cu-phthalocyanine α in aqueous dispersion with color index pigment blue 15: 2/74160, pH 7-10 and density 1.1 to 1.3

5: quinolinone yellow (Chinophthalogel), a well-flowing paste with color index pigment yellow 138/56300, pH 7-10 and density 1.3-1.4

d) Additive agent

1: if a pretreated (see point II) substrate is used, then no aqueous fluoride-containing pretreatment solution is used. Preferably for deposition on aluminum substrates.

2: phosphoric acid as an aqueous solution (20%).

3: the content of antifoam, based on natural oil, emulsifier, and in the form of supply in water, was 1% by weight. The data in the table are based on the amount of solution per liter of formulation.

Additives are preferably used if the pH of the formulation has to be adjusted or a foam has to be formed.

Overview of exemplary formulations used

Table 1: formulation examples of coatings and coating sequences according to the invention

E: washing the organic coating:

rinsing after the organic coating serves to remove non-adhering portions of the formulation and build-up of the formulation and to carry out the process as close to reality as possible, as is customary for industrial applications.

F: drying and crosslinking the coating:

drying or drying to form a film, wherein film formation is also understood in the sense of the present invention as the baking or crosslinking of the coating, in particular of the organic polymer fraction:

1: 20 minutes at 200 ℃

Examples of coating sequences

The examples are not intended to be limiting in this regard and are intended to be illustrative of the following coating sequences on the substrate 2:

example 1

Step I

Step II 120s (15 μm dry film thickness) using the formulation No. 9

Step III 15s

Step II 60s (5 μm dry film thickness) using the formulation number 1

Step III 15s

Step II 80s (10 μm dry film thickness) using preparation No. 10

Step III 15s

Step II 60s (5 μm dry film thickness) using the formulation No. 4

Step III 15s

Step II 60s (5 μm dry film thickness) using the formulation No. 11

Step III 15s

The coating was dried and film formed at 170 ℃ for 10 minutes. A coating of five layers, which is clearly visually distinguishable by the pigment addition, is obtained using three exemplary binders used in the different layers.

Example 2

Step I

Step II 180s (20 μm dry film thickness) using the formulation No. 15

Step III 15s

Step II 60s (20 μm dry film thickness) using the formulation No. 7

Step III 15s

Step II 80s (20 μm dry film thickness) using the formulation No. 16

Step III 15s

The coating was dried and film formed at 170 ℃ for 10 minutes. A coating of three coats is obtained which is clearly visually distinguishable by the pigment addition.

Example 3

Step I

Step II 180s (20 μm dry film thickness) using the formulation No. 3

Step III 15s

Step II 60s (20 μm dry film thickness) using the formulation No. 11

Step III 15s

Step II 80s (20 μm dry film thickness) using the formulation No. 3

Step III 15s

The coating was dried and film formed at 170 ℃ for 10 minutes. A coating of about 60 μm of three coats, visually clearly distinguishable by pigment addition, was obtained.

Claims

1. Process for coating a metal surface of a substrate with an aqueous composition in the form of a dispersion containing at least one stabilised binder and gelling agent and forming an organic coating based on an ionic gel with cations dissolved from the metal surface in a pre-treatment step and/or during contact, in which process the coating is carried out by:

I. providing a substrate having a cleaned metal surface,

contacting and coating a metal surface with a first aqueous composition in the form of a dispersion to form an organic coating,

optionally rinsing the organic coating layer,

optionally drying the organic coating, and

b) adjusting to a pH value of 1 to 7;

g) the tests described under c) and d) were repeated,

the stabilized binder is selected from the group consisting of: non-ionically stabilized polyepoxy dispersions, non-ionically stabilized polyurethane dispersions and ionically stabilized polyacrylate dispersions.

2. The method according to claim 1, wherein the aqueous composition is in the form of a suspension.

3. The method of claim 1, wherein the stabilized binder must satisfy the condition,

g) the tests described under c) and d) were repeated.

4. Method according to claim 1, characterized in that the aqueous composition contains as stabilized binder from 0.01 to 80.0% by weight, based on the total mass of the resulting mixture, of the dispersion and from 0.001 to 20.0% by weight, based on the total mass of the resulting mixture, of at least one gelling agent, wherein the stabilized dispersion has a solids content of from 20 to 90% by weight, a viscosity of from 100 to 5000mPas, a density of from 1.0 to 1.2g/cm³And a pH-value in the range of 0.5 to 10.

5. Method according to claim 3, characterized in that the aqueous composition contains as stabilized binder from 0.01 to 80.0% by weight, based on the total mass of the resulting mixture, of the dispersion and from 0.001 to 20.0% by weight, based on the total mass of the resulting mixture, of at least one gelling agent, wherein the stabilized dispersion has a solids content of from 20 to 90% by weight, a viscosity of from 100 to 5000mPas, a density of from 1.0 to 1.2g/cm³And a pH-value in the range of 0.5 to 10.

6. The method according to any one of claims 1 to 5, characterized in that the aqueous composition additionally contains one or more representatives from the group selected from:

c) a content of at least one defoamer, and

d) at least one additive selected from the group consisting of: pigments, biocides, dispersion aids, film-forming aids, acidic or/and basic aids for adjusting the pH value, thickeners and levelling agents.

7. The method according to any one of claims 1 to 5, characterized in that the gelling agent is selected from: a) at least one polysaccharide based on glycogen, amylose, amylopectin, algin, alginate, pectin, cellulose, chitin, chitosan, dextran, levan, gellan gum, gum arabic, starch, xanthan gum, tragacanth gum, karaya gum, tara gum, and glucomannan; b) at least one anionic polyelectrolyte of natural origin based on polyamino acids, collagen, polypeptides, lignin, or c) at least one synthetic anionic polyelectrolyte based on polyamino acids, polyacrylic acid-copolymers, acrylamide-copolymers, polyvinylsulfonic acid, polycarboxylic acid, polyphosphoric acid, or polystyrene.

8. The method of claim 7, wherein the glucan is selected from the group consisting of guaiacol and curdlan.

9. The method of claim 7, wherein the algin is selected from the group consisting of agar and carrageenan.

10. The method according to any of the preceding claims 1-5, 8 and 9, characterized in that the aqueous composition and the organic coating layer prepared therefrom contain at least one anionic polysaccharide as gelling agent, selected from anionic polysaccharides having a degree of esterification of the carboxyl functions in the range of 5 to 75% based on the total number of alcohol-and carboxyl groups.

11. A method according to claim 7, characterised in that the aqueous composition and the organic coating layer prepared therefrom contain at least one anionic polysaccharide as gelling agent, selected from anionic polysaccharides having a degree of esterification of the carboxyl functions in the range of 5 to 75% based on the total number of alcohol-and carboxyl groups.

12. The method according to any of the preceding claims 1-5, 8 and 9, characterized in that the aqueous composition andthe organic coating thus prepared contains at least one anionic polysaccharide and/or at least one anionic polyelectrolyte as gelling agent, selected from those having a molecular weight of from 500 to 1000000g/mol^-1An anionic polysaccharide and an anionic polyelectrolyte within the range of (1).

13. Process according to claim 7, characterized in that the aqueous composition and the organic coating thus prepared contain at least one anionic polysaccharide and/or at least one anionic polyelectrolyte as gelling agent, selected from those having a molecular weight of between 500 and 1000000g/mol^-1An anionic polysaccharide and an anionic polyelectrolyte within the range of (1).

14. The method according to any of the preceding claims 1-5, 8 and 9, characterized in that the aqueous composition and the organic coating prepared therefrom contain at least one anionic polysaccharide or at least one anionic polyelectrolyte as gelling agent, selected from anionic polysaccharides and anionic polyelectrolytes having a degree of amidation of the carboxyl functions in the range of 1 to 50% or a degree of epoxidation of the carboxyl functions up to 80%.

15. The method according to the preceding claim 7, characterized in that the aqueous composition and the organic coating prepared therefrom contain at least one anionic polysaccharide or at least one anionic polyelectrolyte as gelling agent, selected from anionic polysaccharides and anionic polyelectrolytes having a degree of amidation of the carboxyl functions in the range of 1 to 50% or a degree of epoxidation of the carboxyl functions up to 80%.

16. The method according to claim 7, characterized in that the anionic polyelectrolyte is modified with an adhesion group selected from the group consisting of polyfunctional epoxides, isocyanates, primary amines, secondary amines, tertiary amines, quaternary amines, amides, imides, imidazoles, Michael reaction products, carbodiimides, carbenes, polyfunctional carboxylic acids, nucleic acids, polyacrylic acid derivatives, polyvinyl alcohols, polyphenols, polyols bearing at least one alkyl and/or aryl group, phosphoric acids, sulfonic acids, vinylsulfonic acids, vinylphosphonic acids, silanes and silanols and/or siloxanes formed therefrom, triazines, thiazoles, thiazines, dithiazines, acetals, hemiacetals, quinones, saturated fatty acids, unsaturated fatty acids, alkyds, esters, ethers, diols, anhydrides and acetylacetones, and from β -diketones, carbonyls and hydroxyls.

17. The method according to claim 12, characterized in that the anionic polyelectrolyte is modified with an adhesion group selected from the group consisting of polyfunctional epoxides, isocyanates, primary amines, secondary amines, tertiary amines, quaternary amines, amides, imides, imidazoles, Michael reaction products, carbodiimides, carbenes, polyfunctional carboxylic acids, nucleic acids, polyacrylic acid derivatives, polyvinyl alcohols, polyphenols, polyols bearing at least one alkyl and/or aryl group, phosphoric acids, sulfonic acids, vinylsulfonic acids, vinylphosphonic acids, silanes and silanols and/or siloxanes formed therefrom, triazines, thiazoles, thiazines, dithiazines, acetals, hemiacetals, quinones, saturated fatty acids, unsaturated fatty acids, alkyds, esters, ethers, diols, anhydrides and acetylacetones, and from β -diketones, carbonyls and hydroxyls.

18. The method according to claim 14, characterized in that the anionic polyelectrolyte is modified with an adhesion group selected from the group consisting of polyfunctional epoxides, isocyanates, primary amines, secondary amines, tertiary amines, quaternary amines, amides, imides, imidazoles, Michael reaction products, carbodiimides, carbenes, polyfunctional carboxylic acids, nucleic acids, polyacrylic acid derivatives, polyvinyl alcohols, polyphenols, polyols bearing at least one alkyl and/or aryl group, phosphoric acids, sulfonic acids, vinylsulfonic acids, vinylphosphonic acids, silanes and silanols and/or siloxanes formed therefrom, triazines, thiazoles, thiazines, dithiazines, acetals, hemiacetals, quinones, saturated fatty acids, unsaturated fatty acids, alkyds, esters, ethers, diols, anhydrides and acetylacetones, and from β -diketones, carbonyls and hydroxyls.

19. The method according to claim 7, wherein the anionic polyelectrolyte is modified with an adhesion group selected from the group consisting of polyfunctional epoxides, isocyanates, primary amines, secondary amines, tertiary amines, quaternary amines, imides, imidazoles, formamides, Michael reaction products, carbodiimides, cyclic carbenes, cyclic carbonates, amino acids, nucleic acids, methacrylamides, polyacrylic acids, polyacrylic acid derivatives, polyvinyl alcohols, polyols with at least one alkyl and/or aryl group, caprolactams, phosphoric acids, phosphoric esters, epoxy esters, sulfonic acids, sulfonic esters, vinylsulfonic acids, vinylphosphonic acids, catechols, silanes and silanols and/or siloxanes formed therefrom, triazines, thiazoles, thiazines, dithiazines, acetals, hemiacetals, quinones, saturated fatty acids, unsaturated fatty acids, alkyds, polyesters, diols, cyclic ethers, anhydrides, and acetylacetones, and from β -diketones, carbonyls and hydroxyls.

20. The method according to claim 12, wherein the anionic polyelectrolyte is modified with an adhesion group selected from the group consisting of multifunctional epoxides, isocyanates, primary amines, secondary amines, tertiary amines, quaternary amines, imides, imidazoles, formamides, Michael reaction products, carbodiimides, cyclic carbenes, cyclic carbonates, amino acids, nucleic acids, methacrylamides, polyacrylic acids, polyacrylic acid derivatives, polyvinyl alcohols, polyols with at least one alkyl and/or aryl group, caprolactams, phosphoric acids, phosphoric esters, epoxy esters, sulfonic acids, sulfonic esters, vinylsulfonic acids, vinylphosphonic acids, catechols, silanes and silanols and/or siloxanes formed therefrom, triazines, thiazoles, thiazines, dithiazines, acetals, hemiacetals, quinones, saturated fatty acids, unsaturated fatty acids, alkyds, polyesters, diols, cyclic ethers, anhydrides, and acetylacetones, and from β -diketones, carbonyls and hydroxyls.

21. The method according to claim 14, wherein the anionic polyelectrolyte is modified with an adhesion group selected from the group consisting of multifunctional epoxides, isocyanates, primary amines, secondary amines, tertiary amines, quaternary amines, imides, imidazoles, formamides, Michael reaction products, carbodiimides, cyclic carbenes, cyclic carbonates, amino acids, nucleic acids, methacrylamides, polyacrylic acids, polyacrylic acid derivatives, polyvinyl alcohols, polyols with at least one alkyl and/or aryl group, caprolactams, phosphoric acids, phosphoric esters, epoxy esters, sulfonic acids, sulfonic esters, vinylsulfonic acids, vinylphosphonic acids, catechols, silanes and silanols and/or siloxanes formed therefrom, triazines, thiazoles, thiazines, dithiazines, acetals, hemiacetals, quinones, saturated fatty acids, unsaturated fatty acids, alkyds, polyesters, diols, cyclic ethers, anhydrides, and acetylacetones, and from β -diketones, carbonyls and hydroxyls.

22. Process according to any one of the preceding claims 19 to 21, characterized in that the ether is a crown ether.

23. A method according to any of the preceding claims 1-5, 8, 9, 11, 13 and 15-21, characterized in that the aqueous composition and the organic coating layer prepared therefrom have a content of at least one complexing agent for metal cations.

24. The method of any one of claims 1-5, 8, 9, 11, 13, and 15-21, wherein the aqueous composition and the organic coating produced therefrom have a content of polymer modified to complex metal cations.

25. A method according to claim 23, characterized in that the aqueous composition and the organic coating prepared therefrom have a content of at least one complexing agent selected from complexing agents based on maleic, alendronic, itaconic, citraconic or mesaconic acid or anhydrides or half-esters of these carboxylic acids.

26. A method according to any of the preceding claims 1-5, 8, 9, 11, 13,15-21 and 25, characterized In that the aqueous composition and the organic coating layer prepared therefrom contain at least one type of cation selected from cations based on a salt functioning as a cation selected from melamine salts, nitroso salts, oxonium salts, ammonium salts, salts with quaternary nitrogen cations, salts of ammonium derivatives and metal salts of Ag, Al, Ba, Ca, Co, Cu, Fe, In, Mg, Mn, Mo, Ni, Pb, Sn, Ta, Ti, V, W, Zn and/or Zr.

27. The method according to claim 1, characterized in that the aqueous composition contains complexed titanium fluoride and/or zirconium fluoride in an amount of 0.1 to 30 g/L.

28. The method according to any of the preceding claims 1-5, 8, 9, 11, 13,15-21, 25 and 27, characterized in that the metal surface is pretreated before contacting and coating it with the aqueous composition in process step II.

29. The method of any of the preceding claims 1-5, 8, 9, 11, 13,15-21, 25 and 27, wherein each of the aqueous compositions forms an ionic gel-based organic coating, wherein the coating thickness of all deposited coatings is in the range of 3 to 500 μ ι η and 2 to 10 coatings are deposited after drying and crosslinking all applied coatings.

30. The method of claim 29, wherein the coating thickness of all deposited coatings is in the range of 5 to 300 μm after drying and crosslinking all applied coatings.

31. The method of claim 30, wherein the coating thickness of all deposited coatings is in the range of 8 to 100 μm after drying and crosslinking all applied coatings.

32. Method according to the preceding claim 29, characterized in that 3 to 5 coating layers are deposited.

33. Method according to claim 30 or 31, characterized in that 3 to 5 coating layers are deposited.

34. The method of any of the preceding claims 1-5, 8, 9, 11, 13,15-21, 23, 25, 27 and 30-32, characterized in that each organic coating is formed in the dipping bath within 0.05 to 20 minutes and has a dry film thickness in the range of 1 to 100 μ ι η, respectively, after drying.

35. The method according to claim 34, wherein each organic coating after drying has a dry film thickness in the range of 3 to 60 μ ι η, respectively.

36. The method according to the preceding claim 35, characterized in that each organic coating after drying has a dry film thickness in the range of 5 to 30 μ ι η, respectively.

37. Aqueous composition for use in a method according to any one of claims 1-5, 8, 9, 11, 13,15-21, 23, 25, 27, 30-32, 35 and 36, each consisting of a mixture of at least one dispersion as stabilized binder having a solids content of 30 to 90% by weight, a viscosity of 100 to 5000mPas and a viscosity of 1.0 to 1.2g/cm and a gelling agent³In an amount of from 0.01 to 80.0 wt. -%, based on the total mass of the obtained mixture, and in an amount of from 0.001 to 20.0 wt. -%, based on the total mass of the obtained mixture, wherein the aqueous composition has a pH-value in the range of from 1 to 7, and wherein the at least one stabilized dispersion is selected from: non-ionic stabilizerTailored polyepoxy dispersions, non-ionically stabilized polyurethane dispersions and ionically stabilized polyacrylate dispersions.

38. The aqueous composition according to claim 37, characterized in that it additionally contains one or more representatives selected from the group consisting of:

c) a content of at least one defoamer, and

d) at least one additive selected from the group consisting of: pigments, biocides, dispersion aids, film-forming aids, aids for adjusting the pH value to acidic or/and basic values, thickeners and levelling agents.